US5238896A - Isomerization process and catalyst therefor - Google Patents
Isomerization process and catalyst therefor Download PDFInfo
- Publication number
- US5238896A US5238896A US07/991,845 US99184592A US5238896A US 5238896 A US5238896 A US 5238896A US 99184592 A US99184592 A US 99184592A US 5238896 A US5238896 A US 5238896A
- Authority
- US
- United States
- Prior art keywords
- composition
- accordance
- cucl
- alcl
- matter prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C5/2786—Acids of halogen; Salts thereof
- C07C5/2789—Metal halides; Complexes thereof with organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
- C07C5/271—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously with inorganic acids; with salts or anhydrides of acids
- C07C5/2718—Acids of halogen; Salts thereof; complexes thereof with organic compounds
- C07C5/2721—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- this invention relates to the preparation of a composition of matter which is effective as a catalyst for isomerizing alkanes and cycloalkanes. In another aspect, this invention relates to an alkane/cycloalkane isomerization process.
- alkane isomerization is known and has been described in various scientific articles.
- the present invention is directed to a novel, effective alkane isomerization catalyst composition comprising a combination of aluminum halide(s) and copper(II) salt(s) and a particular solid inorganic refractory material.
- a method of preparing a composition of matter comprises the steps of:
- step (c) removing said at least one alcohol from the shaped particles obtained in step (b) so as to obtain dry shaped particles.
- the at least one aluminum halide is aluminum chloride and the at least one copper(II) salt is cupric chloride.
- the at least one alcohol is ethanol.
- the preferred molar ratio of AlCl 3 to CuCl 2 is about 2:1 to about 3:1.
- the preferred shaping method of step (b) is extrusion.
- composition of matter prepared by the above-described method is provided.
- a process for isomerizing saturated hydrocarbons comprises contacting at least one feed hydrocarbon selected from the group consisting of alkanes containing 4-10 carbon atoms per molecule and cycloalkanes containing 5-10 carbon atoms per molecule with the catalyst composition having been prepared by the above-described preparation method, at such contacting conditions as to convert at least a portion of said at least one feed hydrocarbon to at least one product isomer (having the same number of carbon atoms per molecule as said at least one feed hydrocarbon but having a different structural formula).
- feed hydrocarbon When the feed hydrocarbon is an alkane, concurrently with the isomerization of a portion of the feed alkane, another portion of said feed alkane is generally disproportionated, i.e., converted to a mixture of at least one alkane having a higher number of carbon atoms per molecule and at least one alkane having a lower number of carbon atoms per molecule than said feed alkane(s).
- Presently preferred feed hydrocarbons are normal (straight-chain) C 5 -C 8 alkanes, branched C 5 -C 8 alkanes (isoalkanes) and methyl-substituted C 5 -C 7 cycloalkanes.
- Mixing step (a) in the preparation method of this invention can be carried out in any suitable manner by any suitable, conventional mixing means in the substantial absence of moisture.
- suitable, essentially anhydrous Cu(II) salts are CuCl 2 (most preferred), CuBr 2 , CuI 2 , CuSO 4 , Cu(HSO 4 ) 2 and Cu(NO 3 ) 2 .
- Suitable, essentially anhydrous alcohols which can be employed include (but are not limited to) methanol, ethanol (most preferred), 1-propanol, 2-propanol, isopropanol, butanols, pentanols and hexanols.
- the molar ratio of aluminum halide(s) to copper(II) salt(s) is about 2:1 to about 5:1 (preferably about 2:1 to about 3:1)
- the ratio of the weight of calcium aluminate to the combined weight of aluminum halide(s) and copper(II) salt(s) is about 0.01:1 to about 0.5:1
- the ratio of the weight of alcohol(s) to the combined weight of aluminum halide(s), Cu(II) salt(s) and Ca aluminate is about 0.01:1 to about 0.1:1.
- step (a) it is within the scope of this invention (yet presently not preferred) to have other ingredients present in step (a), such as AII 3 , Al 2 (SO 4 ) 3 , calcium silicate cement, GaCl 3 , and compounds (in particular chlorides and sulfates) of Ti, Zr, Hf, Ta, Cr, Mo, Fe, Co and Ni.
- other ingredients such as AII 3 , Al 2 (SO 4 ) 3 , calcium silicate cement, GaCl 3 , and compounds (in particular chlorides and sulfates) of Ti, Zr, Hf, Ta, Cr, Mo, Fe, Co and Ni.
- Shaping step (b) can be carried out in any suitable manner, such as by extrusion through one die or a plurality of dies, or by pelletizing (e.g., in a rotary mixer) or by tabletting (in a suitable press), preferably in the substantial absence of moisture.
- the size of the obtained shaped particles i.e., the diameter of extruded cylinders or of pellets is about 0.1-2 cm.
- Drying step (c) can be carried out in any suitable manner, preferably in the substantial absence of moisture at a temperature of about 50°-350° C. for a time period of about 0.1-20 hours, more preferably under vacuum conditions (i.e., at a pressure of below 1 atm) and/or in an inert gas atmosphere (e.g., N 2 or He or Ar).
- the dried particles are preferably allowed to cool in a dry inert gas atmosphere.
- the catalyst composition described above is employed for at least partially isomerizing normal (straight-chain) alkanes and/or isoalkanes (i.e., branched alkanes) containing 4-10 carbon atoms per molecule and/or cycloalkanes containing 5-10 carbon atoms.
- alkanes in particular branched alkanes
- a substantial portion of the feed hydrocarbons are generally disproportionated (concurrently with the isomerization).
- Non-limiting examples of suitable feed alkanes are n-butane, isobutane, n-pentane, isopentane (i.e., 2-methylbutane), n-hexane, isohexanes (such as 2-methylpentane, 3-methyl-pentane, 2,2-dimethylbutane), n-heptane, isoheptanes (in particular methyl-substituted hexanes and dimethyl-substituted pentanes), n-octane, isooctanes (in particular methyl-substituted heptanes and dimethyl-substituted hexanes), n-nonane, isononanes (in particular methyl-substituted octanes, dimethyl-substituted heptanes, trimethyl-substituted hexanes), n-decane and isodecanes
- Presently preferred feed alkanes are C 4 -C 8 normal alkanes and C 4 -C 8 isoalkanes.
- the primary objective of the process of this invention is to make highly branched alkanes by isomerization, preferably normal (straight-chain) and monomethyl-substituted feed alkanes are used.
- the objective of the process of this invention is to primarily disproportionate the feed alkanes (i.e., convert them to higher and lower alkanes), preferably branched feed alkanes are used.
- Presently preferred feed alkanes are n-pentane, and 2,2,4-trimethylpentane (isooctane).
- Non-limiting examples of suitable feed cycloalkanes are methylcyclobutane, methylcyclopentane (particularly preferred), methylcyclohexane, dimethylcyclopentanes, dimethylcyclohexanes, trimethylcyclopentanes, methylcycloheptane, dimethylcycloheptanes and trimethylcyclohexanes. Cycloalkanes generally do not disproportionate to any significant extent under the operating conditions of the isomerization process of this invention.
- the process for isomerizing C 4 -C 10 alkanes and/or C 5 -C 10 cycloalkanes with the above-described catalyst composition can be carried out at any suitable reaction conditions, generally at a temperature of up to about 300° C., preferably at about 20°-100° C., more preferably at about 20°-40° C., generally at a pressure of about 1-200 atm.
- the feed alkane(s) and/or cycloalkane(s) can be contacted with the catalyst composition in any suitable mode, such as in a slurry-type operation with the catalyst being dispersed in the feed hydrocarbon(s), or in a fixed catalyst bed operation in which the hydrocarbon feed flows upward or downward through a solid catalyst layer (or several catalyst layers), generally at a liquid hourly space velocity of about 0.1-10 cc hydrocarbon feed per cc catalyst per hour.
- the time of contact between the feed alkane(s) and/or cycloalkane(s) and the catalyst composition generally is in the range of about 5 minutes to about 24 hours, preferably about 0.5-6 hours.
- the isomerization process can be carried out as a batch operation or as a continuous operation.
- the isomerization processes of this invention frequently generates a multitude of products, especially in the case of alkanes which do not only isomerize but also, to a significant extent, disproportionate to higher and lower alkanes.
- This separation can be carried out in any suitable manner, generally by fractional distillation (optionally in the presence of an extractant, i.e., by extractive distillation), as is easily determined by persons skilled in the various liquid-liquid separation technologies.
- This example illustrates the preparation of various isomerization catalyst compositions from AlCl 3 and CuCl 2 .
- Catalyst A (Control) was prepared by manually mixing 100 grams of AlCl 3 , 50 grams of CuCl 2 and 4.5 mL of dry ethanol, and extruding the mixture through a laboratory extruder equipped with an aluminum die plate having twelve 1/16 inch holes. Both preparation steps were carried out in a glove bag under a dry nitrogen atmosphere. The obtained extrudates were dried for 7 hours under vacuum conditions at 65°-70° C., followed by a dry nitrogen gas purge. The average crush strength of the dry extrudates, measured on a laboratory crush strength apparatus equipped with two metal plates of 1/8 inch diameter and a 0-30 lb. force gauge, was 5.8 lb. per particle.
- Catalyst B (Control) was prepared by manually mixing 80 grams of AlCl 3 , 40 grams of CuCl 2 , 30 grams of gamma-alumina (provided by Degussa Corporation, Allendale, N.J., under the product designation of Aluminum Oxide C) and 5 mL of dry ethanol in a glove bag under a dry nitrogen gas atmosphere. The mixture was extruded and dried, essentially in accordance with the procedure described for Catalyst A. The average crush strength of Catalyst B extrudates was 9.3 lb. per particle.
- Catalyst C (Invention) was prepared by manually mixing 100 grams (about 0.75 mole) of AlCl 3 , 40 grams (about 0.30 mole) of CuCl 2 , 7 grams of calcium aluminate (provided by Lafarge Calcium Aluminates, Chesapeake, Va., under the product designation of Secar 71) and 5 mL of dry ethanol. The mixture was extruded through a 1/4" aluminum die plate containing ten 1/16 inch holes. Both preparation steps were carried out in a glove bag under a dry nitrogen atmosphere. The extrudates were dried overnight at 150° C. under vacuum conditions, followed by a dry nitrogen gas purge. The average crush of Catalyst C particles was 1.7 lb. per particle.
- This example illustrates the performance of the catalysts described in Example I for the conversion of a normal alkane.
- Example II illustrates the performance of the catalysts described in Example I for the conversion of an isoalkane.
- 10 mL of an isooctane (2,2,4-trimethylpentane) and 5 grams of Catalysts A, B and C were placed in a sealed glass tube at about 24° C. Samples of the reaction mixture were withdrawn after 1 hour and analyzed by means of a gas chromatograph. Test results are summarized in Table II.
- Example II illustrates the performance of the catalysts described in Example I for the conversion of methylcyclopentane to cyclohexane at about 23° C., essentially in accordance with the procedure described in Example II. Test results summarized below in Table III demonstrate the superiority of Invention Catalyst C.
Abstract
A composition is prepared by mixing at least one aluminum halide (preferably AlCl3), at least one copper(II) salt (preferably CuCl2), calcium aluminate and at least one alcohol (preferably ethanol), shaping the mixture, and drying the shaped particles. The thus-obtained catalyst composition can be employed as a catalyst in the isomerization of alkanes and/or cycloalkanes.
Description
This is a division of application Ser. No. 07/941,360, filed Sep. 4, 1992, now U.S. Pat. No. 5,202,519.
In one aspect, this invention relates to the preparation of a composition of matter which is effective as a catalyst for isomerizing alkanes and cycloalkanes. In another aspect, this invention relates to an alkane/cycloalkane isomerization process.
The use of combinations of aluminum halide (in particular AlCl3) and certain metal chlorides and sulfates (in particular CuCl2 or CuSO4) for alkane isomerization is known and has been described in various scientific articles. The present invention is directed to a novel, effective alkane isomerization catalyst composition comprising a combination of aluminum halide(s) and copper(II) salt(s) and a particular solid inorganic refractory material.
It is an object of this invention to provide a method of preparing a catalyst composition from aluminum halide(s), copper(II) salt(s) and a solid inorganic support material. It is another object of this invention to provide a catalyst composition prepared by this process. It is a further object of this invention to employ this catalyst composition in a process for isomerizing alkanes and/or cycloalkanes. Other objects and advantages will be apparent from the detailed description of the invention and the appended claims.
In accordance with this invention, a method of preparing a composition of matter (effective as an alkane and/or cycloalkane isomerization catalyst composition) comprises the steps of:
(a) mixing, in the substantial absence of water, at least one aluminum halide selected from the group consisting of AlCl3 and AlBr3, at least one copper(II) salt, calcium aluminate and at least one alcohol containing 1-12 carbon atoms per molecule, at a molar ratio of said at least one aluminum halide to said at least one copper(II) salt in excess of about 1:1;
(b) shaping the mixture obtained in step (a); and
(c) removing said at least one alcohol from the shaped particles obtained in step (b) so as to obtain dry shaped particles.
Preferably, the at least one aluminum halide is aluminum chloride and the at least one copper(II) salt is cupric chloride. Also preferably, the at least one alcohol is ethanol. The preferred molar ratio of AlCl3 to CuCl2 is about 2:1 to about 3:1. The preferred shaping method of step (b) is extrusion.
Also in accordance with this invention, a composition of matter prepared by the above-described method is provided.
Further in accordance with this invention, a process for isomerizing saturated hydrocarbons comprises contacting at least one feed hydrocarbon selected from the group consisting of alkanes containing 4-10 carbon atoms per molecule and cycloalkanes containing 5-10 carbon atoms per molecule with the catalyst composition having been prepared by the above-described preparation method, at such contacting conditions as to convert at least a portion of said at least one feed hydrocarbon to at least one product isomer (having the same number of carbon atoms per molecule as said at least one feed hydrocarbon but having a different structural formula). When the feed hydrocarbon is an alkane, concurrently with the isomerization of a portion of the feed alkane, another portion of said feed alkane is generally disproportionated, i.e., converted to a mixture of at least one alkane having a higher number of carbon atoms per molecule and at least one alkane having a lower number of carbon atoms per molecule than said feed alkane(s). Presently preferred feed hydrocarbons are normal (straight-chain) C5 -C8 alkanes, branched C5 -C8 alkanes (isoalkanes) and methyl-substituted C5 -C7 cycloalkanes.
Mixing step (a) in the preparation method of this invention can be carried out in any suitable manner by any suitable, conventional mixing means in the substantial absence of moisture. Non-limiting examples of suitable, essentially anhydrous Cu(II) salts are CuCl2 (most preferred), CuBr2, CuI2, CuSO4, Cu(HSO4)2 and Cu(NO3)2. Suitable, essentially anhydrous alcohols which can be employed include (but are not limited to) methanol, ethanol (most preferred), 1-propanol, 2-propanol, isopropanol, butanols, pentanols and hexanols.
Generally, the molar ratio of aluminum halide(s) to copper(II) salt(s) is about 2:1 to about 5:1 (preferably about 2:1 to about 3:1), the ratio of the weight of calcium aluminate to the combined weight of aluminum halide(s) and copper(II) salt(s) is about 0.01:1 to about 0.5:1, and the ratio of the weight of alcohol(s) to the combined weight of aluminum halide(s), Cu(II) salt(s) and Ca aluminate is about 0.01:1 to about 0.1:1. It is within the scope of this invention (yet presently not preferred) to have other ingredients present in step (a), such as AII3, Al2 (SO4)3, calcium silicate cement, GaCl3, and compounds (in particular chlorides and sulfates) of Ti, Zr, Hf, Ta, Cr, Mo, Fe, Co and Ni.
Shaping step (b) can be carried out in any suitable manner, such as by extrusion through one die or a plurality of dies, or by pelletizing (e.g., in a rotary mixer) or by tabletting (in a suitable press), preferably in the substantial absence of moisture. Generally, the size of the obtained shaped particles (i.e., the diameter of extruded cylinders or of pellets) is about 0.1-2 cm.
Drying step (c) can be carried out in any suitable manner, preferably in the substantial absence of moisture at a temperature of about 50°-350° C. for a time period of about 0.1-20 hours, more preferably under vacuum conditions (i.e., at a pressure of below 1 atm) and/or in an inert gas atmosphere (e.g., N2 or He or Ar). The dried particles are preferably allowed to cool in a dry inert gas atmosphere.
Also in accordance with this invention, the catalyst composition described above is employed for at least partially isomerizing normal (straight-chain) alkanes and/or isoalkanes (i.e., branched alkanes) containing 4-10 carbon atoms per molecule and/or cycloalkanes containing 5-10 carbon atoms. When alkanes (in particular branched alkanes) are employed as feed hydrocarbons, a substantial portion of the feed hydrocarbons are generally disproportionated (concurrently with the isomerization). Non-limiting examples of suitable feed alkanes are n-butane, isobutane, n-pentane, isopentane (i.e., 2-methylbutane), n-hexane, isohexanes (such as 2-methylpentane, 3-methyl-pentane, 2,2-dimethylbutane), n-heptane, isoheptanes (in particular methyl-substituted hexanes and dimethyl-substituted pentanes), n-octane, isooctanes (in particular methyl-substituted heptanes and dimethyl-substituted hexanes), n-nonane, isononanes (in particular methyl-substituted octanes, dimethyl-substituted heptanes, trimethyl-substituted hexanes), n-decane and isodecanes (in particular methyl-substituted nonanes, dimethyl-substituted octanes, trimethyl-substituted heptanes, tetramethyl-substituted hexanes). Presently preferred feed alkanes are C4 -C8 normal alkanes and C4 -C8 isoalkanes. When the primary objective of the process of this invention is to make highly branched alkanes by isomerization, preferably normal (straight-chain) and monomethyl-substituted feed alkanes are used. However, when the objective of the process of this invention is to primarily disproportionate the feed alkanes (i.e., convert them to higher and lower alkanes), preferably branched feed alkanes are used. Presently preferred feed alkanes are n-pentane, and 2,2,4-trimethylpentane (isooctane).
Non-limiting examples of suitable feed cycloalkanes are methylcyclobutane, methylcyclopentane (particularly preferred), methylcyclohexane, dimethylcyclopentanes, dimethylcyclohexanes, trimethylcyclopentanes, methylcycloheptane, dimethylcycloheptanes and trimethylcyclohexanes. Cycloalkanes generally do not disproportionate to any significant extent under the operating conditions of the isomerization process of this invention.
The process for isomerizing C4 -C10 alkanes and/or C5 -C10 cycloalkanes with the above-described catalyst composition can be carried out at any suitable reaction conditions, generally at a temperature of up to about 300° C., preferably at about 20°-100° C., more preferably at about 20°-40° C., generally at a pressure of about 1-200 atm. The feed alkane(s) and/or cycloalkane(s) can be contacted with the catalyst composition in any suitable mode, such as in a slurry-type operation with the catalyst being dispersed in the feed hydrocarbon(s), or in a fixed catalyst bed operation in which the hydrocarbon feed flows upward or downward through a solid catalyst layer (or several catalyst layers), generally at a liquid hourly space velocity of about 0.1-10 cc hydrocarbon feed per cc catalyst per hour. The time of contact between the feed alkane(s) and/or cycloalkane(s) and the catalyst composition generally is in the range of about 5 minutes to about 24 hours, preferably about 0.5-6 hours. The isomerization process can be carried out as a batch operation or as a continuous operation.
The isomerization processes of this invention frequently generates a multitude of products, especially in the case of alkanes which do not only isomerize but also, to a significant extent, disproportionate to higher and lower alkanes. Thus, it is generally necessary to separate the various formed hydrocarbon products from one another and from unconverted feed hydrocarbon(s). This separation can be carried out in any suitable manner, generally by fractional distillation (optionally in the presence of an extractant, i.e., by extractive distillation), as is easily determined by persons skilled in the various liquid-liquid separation technologies.
The following examples are provided to further illustrate the processes of this invention, and are not to be construed as unduly limiting the scope of this invention.
This example illustrates the preparation of various isomerization catalyst compositions from AlCl3 and CuCl2.
Catalyst A (Control) was prepared by manually mixing 100 grams of AlCl3, 50 grams of CuCl2 and 4.5 mL of dry ethanol, and extruding the mixture through a laboratory extruder equipped with an aluminum die plate having twelve 1/16 inch holes. Both preparation steps were carried out in a glove bag under a dry nitrogen atmosphere. The obtained extrudates were dried for 7 hours under vacuum conditions at 65°-70° C., followed by a dry nitrogen gas purge. The average crush strength of the dry extrudates, measured on a laboratory crush strength apparatus equipped with two metal plates of 1/8 inch diameter and a 0-30 lb. force gauge, was 5.8 lb. per particle.
Catalyst B (Control) was prepared by manually mixing 80 grams of AlCl3, 40 grams of CuCl2, 30 grams of gamma-alumina (provided by Degussa Corporation, Allendale, N.J., under the product designation of Aluminum Oxide C) and 5 mL of dry ethanol in a glove bag under a dry nitrogen gas atmosphere. The mixture was extruded and dried, essentially in accordance with the procedure described for Catalyst A. The average crush strength of Catalyst B extrudates was 9.3 lb. per particle.
Catalyst C (Invention) was prepared by manually mixing 100 grams (about 0.75 mole) of AlCl3, 40 grams (about 0.30 mole) of CuCl2, 7 grams of calcium aluminate (provided by Lafarge Calcium Aluminates, Chesapeake, Va., under the product designation of Secar 71) and 5 mL of dry ethanol. The mixture was extruded through a 1/4" aluminum die plate containing ten 1/16 inch holes. Both preparation steps were carried out in a glove bag under a dry nitrogen atmosphere. The extrudates were dried overnight at 150° C. under vacuum conditions, followed by a dry nitrogen gas purge. The average crush of Catalyst C particles was 1.7 lb. per particle.
This example illustrates the performance of the catalysts described in Example I for the conversion of a normal alkane.
In one test series, 2 mL n-pentane and 1.0 grams of Catalysts A, B and C were placed in sealed glass tubes at about 24° C. Samples of the liquid reaction mixture were withdrawn at certain time intervals and analyzed by means of a conventional gas chromatograph. Test results are summarized in Table I.
TABLE I ______________________________________ Reaction % Conversion Catalyst Time (Hours) of n-Pentane ______________________________________ A (Control) 1 1.6 4 35.5 24 82.0 B (Control) 1 2.5 4 5.7 24 12.0 C (Invention) 1 71.5 4 92.0 24 95.5 ______________________________________
The above test data clearly show the superiority of invention Catalyst C containing Ca aluminate over the two other AlCl3 /CuCl2 -containing catalysts. In all three test runs, the formed product hydrocarbons were primarily isopentane (2-methylbutane) and isohexanes (2,2-dimethylbutane, 2-methylpentane, 3-methylpentane). Smaller amounts of other identified hydrocarbon products were those of isobutane, isoheptanes (in particular 2,2 and 2,4-dimethylpentanes, 3-ethylpentane and 2-methylhexane) and C7 + alkanes. Thus, while a substantial portion of n-pentane was isomerized to isopentane, an even greater portion of the feed n-pentane had been converted to C6, C7 + and C4 alkanes (probably by a combination of disproportionation, cracking and alkylation reactions).
This example illustrates the performance of the catalysts described in Example I for the conversion of an isoalkane. 10 mL of an isooctane (2,2,4-trimethylpentane) and 5 grams of Catalysts A, B and C were placed in a sealed glass tube at about 24° C. Samples of the reaction mixture were withdrawn after 1 hour and analyzed by means of a gas chromatograph. Test results are summarized in Table II.
TABLE II ______________________________________ Reaction % Conversion Catalyst Time (Hours) of Isooctane ______________________________________ A (Control) 1 34.5 B (Control) 1 3.0 C (Invention) 1 54.6 ______________________________________
Test results in Table II clearly demonstrate the superiority of Catalyst C over Catalysts A and B. In all three test runs, the reaction product contained unconverted feed isooctane (i.e., 2,2,4-trimethylpentane), other isooctanes (in particular 2,3-, 2,4- and 2,5-dimethylhexane and trimethylpentanes), isononanes (in particular trimethylhexanes and dimethylheptanes), and C4 -C7 isoalkanes (in particular isobutane, 2-methylbutane, 2,4-dimethylbutane, 2,4-dimethylpentane and 2-methylhexane). Thus, besides the isomerization of the feed isooctane to other C8 isomers, a substantial portion of the feed isooctanes had been converted to higher and lower isoalkanes (probably by a combination of disproportionation, cracking and alkylation reactions).
This example illustrates the performance of the catalysts described in Example I for the conversion of methylcyclopentane to cyclohexane at about 23° C., essentially in accordance with the procedure described in Example II. Test results summarized below in Table III demonstrate the superiority of Invention Catalyst C.
TABLE III ______________________________________ Reaction % Conversion of Catalyst Time (Hours) Methylcyclopentane ______________________________________ A (Control) 1 0.7 4 1.3 24 12.8 B (Control) 1 1.5 4 7.3 24 22.4 C (Invention) 1 65.8 4 87.3 24 90.1 ______________________________________ Note: The formed products consisted essentially of cyclohexane.
Reasonable variations, modifications and adaptations for various conditions and reactants can be made within the scope of the disclosure and the appended claims without departing from the scope of this invention.
Claims (20)
1. A method of preparing a composition of matter comprising the steps of:
(a) mixing at least one aluminum halide selected from the group consisting of AlCl3 and AlBr3 with at least one copper(II) salt, calcium aluminate and at least one alcohol containing 1-12 carbon atoms per molecule, at a molar ratio of said at least one aluminum halide to said at least one copper(II) salt in excess of about 1:1;
(b) shaping the mixture obtained in step (a); and
(c) removing said at least one alcohol from the shaped particles obtained in step (b) so as to obtain dry shaped particles.
2. A method in accordance with claim 1, wherein said at least one copper(II) salt is selected from the group consisting of CuCl2, CuBr2, CuI2, CuSO4, Cu(HSO4)2 , and Cu(NO3)2, and said at least one alcohol is selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, isopropanol, butanols, pentanols and hexanols.
3. A method in accordance with claim 1, wherein said at least one aluminum halide is AlCl3, said at least one copper(II) salt is CuCl2, said at least one alcohol is ethanol, and step (a) is carried out in the substantial absence of moisture.
4. A method in accordance with claim 3, wherein the molar ratio of AlCl3 to CuCl2 is about 2:1 to about 5:1, the ratio of the weight of calcium aluminate to the combined weight of AlCl3 and CuCl2 is about 0.01:1 to about 0.5:1, and the ratio of the weight of ethanol to the combined weight of AlCl3, CuCl2 and calcium aluminate is 0.01:1 to about 0.1:1.
5. A method in accordance with claim 4, wherein said molar ratio of AlCl3 to CuCl2 is about 2:1 to about 3:1.
6. A method in accordance with claim 3, wherein shaping step (b) is extrusion in the substantial absence of moisture.
7. A method in accordance with claim 3, wherein said shaping step (b) is tabletting in the substantial absence of moisture.
8. A method in accordance with claim 3, wherein step (c) is carried out at a temperature of about 50°-350° C. in the substantial absence of moisture.
9. A method in accordance with claim 8, wherein step (c) is carried out for about 0.1-20 hours.
10. A method in accordance with claim 9, wherein step (c) is carried out under vacuum conditions or, alternatively, in an inert gas atmosphere.
11. A composition of matter prepared by the method of claim 1.
12. A composition of matter prepared by the method of claim 2.
13. A composition of matter prepared by the method of claim 3.
14. A composition of matter prepared by the method of claim 4.
15. A composition of matter prepared by the method of claim 5.
16. A composition of matter prepared by the method of claim 6.
17. A composition of matter prepared by the method of claim 7.
18. A composition of matter prepared by the method of claim 8.
19. A composition of matter prepared by the method of claim 9.
20. A composition prepared by the method of claim 11, wherein the size of the dry shaped particles obtained in step (c) is about 0.1-2 cm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/991,845 US5238896A (en) | 1992-09-04 | 1992-12-16 | Isomerization process and catalyst therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/941,360 US5202519A (en) | 1992-09-04 | 1992-09-04 | Isomerization process and catalyst therefor |
US07/991,845 US5238896A (en) | 1992-09-04 | 1992-12-16 | Isomerization process and catalyst therefor |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/941,360 Division US5202519A (en) | 1992-09-04 | 1992-09-04 | Isomerization process and catalyst therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
US5238896A true US5238896A (en) | 1993-08-24 |
Family
ID=27130155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/991,845 Expired - Fee Related US5238896A (en) | 1992-09-04 | 1992-12-16 | Isomerization process and catalyst therefor |
Country Status (1)
Country | Link |
---|---|
US (1) | US5238896A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5358919A (en) * | 1993-02-03 | 1994-10-25 | Phillips Petroleum Company | Preparation and use of isomerization catalysts |
US20080269045A1 (en) * | 2002-07-24 | 2008-10-30 | Newton Jeffrey P | Production of lower molecular weight hydrocarbons |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2820074A (en) * | 1954-10-19 | 1958-01-14 | Universal Oil Prod Co | Alkylation process |
US3238272A (en) * | 1964-07-01 | 1966-03-01 | Universal Oil Prod Co | Hydrocarbon conversion process and catalyst therefor |
US3248343A (en) * | 1964-04-07 | 1966-04-26 | Standard Oil Co | Hydrocarbon conversion catalyst |
US3420909A (en) * | 1967-08-21 | 1969-01-07 | Universal Oil Prod Co | Alkylation process |
US3502735A (en) * | 1966-08-19 | 1970-03-24 | Harry B Copelin | Process for isomerizing dihalohydrocarbons |
US3631211A (en) * | 1970-04-20 | 1971-12-28 | Universal Oil Prod Co | Preparation of gem-diarylalkanes |
US3655797A (en) * | 1970-09-24 | 1972-04-11 | Universal Oil Prod Co | Alkylation process |
US3760021A (en) * | 1971-08-13 | 1973-09-18 | Exxon Research Engineering Co | Alkylation catalyst |
US3846503A (en) * | 1972-05-30 | 1974-11-05 | Universal Oil Prod Co | Saturated hydrocarbon isomerization process |
-
1992
- 1992-12-16 US US07/991,845 patent/US5238896A/en not_active Expired - Fee Related
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2820074A (en) * | 1954-10-19 | 1958-01-14 | Universal Oil Prod Co | Alkylation process |
US3248343A (en) * | 1964-04-07 | 1966-04-26 | Standard Oil Co | Hydrocarbon conversion catalyst |
US3238272A (en) * | 1964-07-01 | 1966-03-01 | Universal Oil Prod Co | Hydrocarbon conversion process and catalyst therefor |
US3502735A (en) * | 1966-08-19 | 1970-03-24 | Harry B Copelin | Process for isomerizing dihalohydrocarbons |
US3420909A (en) * | 1967-08-21 | 1969-01-07 | Universal Oil Prod Co | Alkylation process |
US3631211A (en) * | 1970-04-20 | 1971-12-28 | Universal Oil Prod Co | Preparation of gem-diarylalkanes |
US3655797A (en) * | 1970-09-24 | 1972-04-11 | Universal Oil Prod Co | Alkylation process |
US3760021A (en) * | 1971-08-13 | 1973-09-18 | Exxon Research Engineering Co | Alkylation catalyst |
US3846503A (en) * | 1972-05-30 | 1974-11-05 | Universal Oil Prod Co | Saturated hydrocarbon isomerization process |
Non-Patent Citations (12)
Title |
---|
N. Kitajima et al., "Cu(AlCl4)2 as a Catalyst for the Isomerization of Pentane at Room Temperature", Journal of Molecular Catalysis 10 (1981), pp. 121-122. |
N. Kitajima et al., "On the Active Species of Aluminum(III) Bromide-Copper(II) Bromide Mixtures as Catalysts for the Isomerization of Pentane", Journal Chem. Society, Perkin Transactions II, 1980, pp. 1201-1205. |
N. Kitajima et al., Cu(AlCl 4 ) 2 as a Catalyst for the Isomerization of Pentane at Room Temperature , Journal of Molecular Catalysis 10 (1981), pp. 121 122. * |
N. Kitajima et al., On the Active Species of Aluminum(III) Bromide Copper(II) Bromide Mixtures as Catalysts for the Isomerization of Pentane , Journal Chem. Society, Perkin Transactions II, 1980, pp. 1201 1205. * |
N. Kitajima, "Two Component Friedel-Crafts Catalysts as Solid Superacids", Materials Chemistry and Physics 17 (1987), pp. 31-48. |
N. Kitajima, Two Component Friedel Crafts Catalysts as Solid Superacids , Materials Chemistry and Physics 17 (1987), pp. 31 48. * |
Y. Ono et al., "Highly Selective Isomerization of Pentane with AlBr3 -Metal Sulfate Mixtures", Chemistry Letters, 1978, pp. 1061-1064. |
Y. Ono et al., "Isomerization of Pentane with AlCl3 --CuSO4 Mixtures", Journal of Catalysis 64 (1980), pp. 13-17. |
Y. Ono et al., "Isomerization of Pentane with Aluminum Chloride (Gallium Chloride)-Cupric Salt Complexes", Proceedings 7th Internat. Congress Catalys., Tokyo, 1980, pp. 1006-1017. |
Y. Ono et al., Highly Selective Isomerization of Pentane with AlBr 3 Metal Sulfate Mixtures , Chemistry Letters, 1978, pp. 1061 1064. * |
Y. Ono et al., Isomerization of Pentane with AlCl 3 CuSO 4 Mixtures , Journal of Catalysis 64 (1980), pp. 13 17. * |
Y. Ono et al., Isomerization of Pentane with Aluminum Chloride (Gallium Chloride) Cupric Salt Complexes , Proceedings 7th Internat. Congress Catalys., Tokyo, 1980, pp. 1006 1017. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5358919A (en) * | 1993-02-03 | 1994-10-25 | Phillips Petroleum Company | Preparation and use of isomerization catalysts |
US20080269045A1 (en) * | 2002-07-24 | 2008-10-30 | Newton Jeffrey P | Production of lower molecular weight hydrocarbons |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR870001515B1 (en) | A catalyat composite converting a hydrocarbon | |
US4939110A (en) | Catalyst for the isomerization of aromatics | |
CA2104822C (en) | Mgapso molecular sieve and use thereof | |
US5233119A (en) | Alkylation process and catalyst therefor | |
WO2005016855A2 (en) | Supported ionic liquid and the use thereof in the disproportionation of isopentane | |
US5202519A (en) | Isomerization process and catalyst therefor | |
US2265548A (en) | Process for the production of isobutane | |
US5238896A (en) | Isomerization process and catalyst therefor | |
US5336830A (en) | Dehydroisomerisation catalyst and its use in the preparation of isobutene from N-butane | |
US3201494A (en) | Hexafluoroantimonic acid-catalyzed hydrocarbon conversions | |
US3855346A (en) | Isomerization of paraffinic hydrocarbons with trifluoromethanesulfonic acid | |
US2885452A (en) | De-arylation of polyarylalkanes | |
US5030770A (en) | Process for the preparation of thymol | |
US5245103A (en) | Isomerization processes and catalysts therefor | |
US3875253A (en) | Dehydrogenating normal paraffins | |
US3340317A (en) | Isomerization of cyclodiolefins | |
US3248443A (en) | Process for alkylating aromatic hydrocarbons | |
US5087785A (en) | Processes for preparing alkylated indanes and tetrahydronaphthalenes | |
US5254794A (en) | Isomerization catalysts and preparation thereof | |
US4877910A (en) | Process for preparing polyalkyl tetrahydronaphthalenes | |
US5349116A (en) | Alkane alkylation and catalyst therefor | |
US4400574A (en) | Isomerization catalyst and process for production thereof | |
US5053558A (en) | Process for the isomerization of cresols | |
US5574201A (en) | Alkylation process | |
US4179581A (en) | Paraffinic hydrocarbon isomerization process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20010824 |
|
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |